Efficient Synthesis of Cyclic Poly(ethylene glycol)s under High Concentration Conditions by the Assistance of Pseudopolyrotaxane with Cyclodextrin Derivatives.

An efficient synthesis of cyclic polymers (CPs) is in high demand due to their unique properties. However, polymer cyclization generally occurs at low concentrations (0.1 g/L), and the synthesis of CPs at high concentrations remains a challenge. Herein an efficient cyclization of poly(ethylene glycol) (Mn = 2000 g/mol, 4000 g/mol) (PEG-2k, PEG-4k) in high concentration (80 g/L) is realized by the assistance of pseudopolyrotaxane (pPRx). Water-soluble pPRx with a U-like-shape inclusion motif is prepared by mixing the 2-hydroxypropyl-γ-cyclodextrin (HPγCD) and PEG with (E)-3,4,5-trimethoxycinnamate (TCA-PEG-2k, TCA-PEG-4k). Subsequent irradiation of the pPRx solution (10-80 g/L) by UV light gives cyclic polymers through the intramolecular [2 + 2] photocycloaddition of the cinnamoyl moieties. The photoreaction of TCA-PEG-2k in the pPRx system gives cyclic monomers (C-1mer) as major products with a yield of 66% at 80 g/L. Additionally, the cyclization of TCA-PEG-4k also gives C-1mer as major products with a yield of 45% at a concentration of 80 g/L.

Leaf-Inspired Host-Guest Complexation-Dictating Supramolecular Gas Sensors.

We report unique conductive leaf-inspired (in particular, stomata-inspired) supramolecular gas sensors in which acetylated cyclodextrin derivatives rule the electric output. The gas sensors consist of polymers bearing acetylated cyclodextrin, adamantane, and carbon black. Host-guest complexes between acetylated cyclodextrin and adamantane corresponding to the closed stomata realize a flexible polymeric matrix. Effective recombination of the cross-links contributes to the robustness. As gas sensors, the supramolecular materials detect ammonia as well as various other gases at 1 ppm in 10 min. The free acetylated cyclodextrin corresponding to open stomata recognized the guest gases to alter the electric resistivity. Interestingly, the conductive device failed to detect ammonia gases at all without acetylated cyclodextrin. The molecular recognition was studied by molecular dynamics simulations. The gas molecules existed stably in the cavity of free acetylated cyclodextrin. These findings show the potential for developing wearable gas sensors.

A genome-wide association and fine-mapping study of white rust resistance in hexaploid chrysanthemum cultivars with a wild diploid reference genome.

White rust caused by Puccinia horiana is one of the most serious diseases of chrysanthemum (Chrysanthemum × morifolium). In this study, we report the DNA markers associated with resistance against P. horiana via a simple approach using the genome of a wild diploid relative, Chrysanthemum seticuspe. First, we identified the important region of the genome in the resistant cultivar "Ariesu" via a genome-wide association study. Simplex single nucleotide polymorphism (SNP) markers mined from ddRAD-Seq were used in a biparental population originating from crosses between resistant "Ariesu" and susceptible "Yellow Queen". The C. seticuspe genome was used as a reference. For the fine mapping of P. horiana resistance locus 2 (Phr2), a comparative whole genome sequencing study was conducted. Although the genome sequences of chrysanthemum cultivars assembled via the short-read approach were fragmented, reliable genome alignments were reconstructed by mapping onto the chromosome level of the C. seticuspe pseudomolecule. Base variants were then identified by comparing the assembled genome sequences of resistant "Ariesu" and susceptible "Yellow Queen". Consequently, SNP markers that were closer to Phr2 compared with ddRAD-Seq markers were obtained. These SNP markers co-segregated with resistance in F1 progenies originating from resistant "Ariesu" and showed robust transferability for detecting Phr2-conferring resistance among chrysanthemum genetic resources. The wild C. seticuspe pseudomolecule, a de facto monoploid genome used for ddRAD-Seq analysis and assembled genome sequence comparison, demonstrated this method's utility as a model for developing DNA markers in hexaploid chrysanthemum cultivars.

Multi-energy dissipation mechanisms in supramolecular hydrogels with fast and slow relaxation modes.

Reversible cross-links by non-covalent bonds have been widely used to produce supramolecular hydrogels that are both tough and functional. While various supramolecular hydrogels with several kinds of reversible cross-links have been designed for many years, a universal design that would allow control of mechanical and functional properties remains unavailable. The physical properties of reversible cross-links are usually quantified by thermodynamics, dynamics, and bond energies. Herein, we investigated the relationship between the molecular mobility and mechanical toughness of supramolecular hydrogels consisting of two kinetically distinct reversible cross-links via host-guest interactions. The molecular mobility was quantified as the second-order average relaxation time (〈τ〉w) of the reversible cross-links. We discovered that hydrogels combining fast (〈τ〉w = 1.8 or 18 s) and slowly (〈τ〉w = 6.6 × 103 or 9.5 × 103 s) reversible cross-links showed increased toughness compared to hydrogels with only one type of cross-link because relaxation processes in the former occurred with wide timescales.

Synergetic improvement in the mechanical properties of polyurethanes with movable crosslinking and hydrogen bonds.

Polyurethane (PU) materials with movable crosslinking were prepared by a typical two-step synthetic process using an acetylated γ-cyclodextrin (TAcγCD) diol compound. The soft segment of PU is polytetrahydrofuran (PTHF), and the hard segment consists of hexamethylene diisocyanate (HDI) and 1,3-propylene glycol (POD). The synthesized PU materials exhibited the typical mechanical characteristics of a movable crosslinking network, and the presence of hydrogen bonds from the urethane bonds resulted in a synergistic effect. Two kinds of noncovalent bond crosslinking increased the Young's modulus of the material without affecting its toughness. Fourier transform infrared spectroscopy and X-ray scattering measurements were performed to analyze the effect of introducing movable crosslinking on the internal hydrogen bond and the microphase separation structure of PU, and the results showed that the carbonyl groups on TAcγCD could form hydrogen bonds with the PU chains and that the introduction of movable crosslinking weakened the hydrogen bonds between the hard segments of PU. When stretched, the movable crosslinking of the PU materials suppressed the orientation of polymer chains (shish-kebab orientation) in the tensile direction. The mechanical properties of the movable crosslinked PU materials show promise for future application in the industrial field.

Control of Photoinduced Electron Transfer Using Complex Formation of Water-Soluble Porphyrin and Polyvinylpyrrolidone.

Inspired by the natural photosynthetic system in which proteins control the electron transfer from electron donors to acceptors, in this research, artificial polymers were tried to achieve this control effect. Polyvinylpyrrolidone (PVP) was found to form complex with pigments 5,10,15,20-tetrakis-(4-sulfonatophenyl) porphyrin (TPPS) and its zinc complex (ZnTPPS) quantitatively through different interactions (hydrogen bonds and coordination bonds, respectively). These complex formations hinder the interaction between ground-state TPPS or ZnTPPS and an electron acceptor (methyl viologen, MV2+) and could control the photoinduced electron transfer from TPPS or ZnTPPS to MV2+, giving more electron transfer products methyl viologen cationic radical (MV+•). Other polymers such as PEG did not show similar results, indicating that PVP plays an important role in controlling the photoinduced electron transfer.

Development of an SSR marker-based genetic linkage map and identification of a QTL associated with flowering time in Eustoma.

Lisianthus (Eustoma grandiflorum) is an important floricultural crop cultivated worldwide. Despite its commercial importance, few DNA markers are available for molecular genetic research. In this study, we constructed a genetic linkage map and to detect quantitative trait loci (QTLs) for important agronomic traits of lisianthus. To develop simple sequence repeat (SSR) markers, we used 454-pyrosequencing technology to obtain genomic shotgun sequences and subsequently identified 8263 putative SSRs. A total of 3990 primer pairs were designed in silico and 1189 unique primer pairs were extracted through a BLAST search. Amplification was successful for more than 1000 primer pairs, and ultimately 278 SSR markers exhibited polymorphism between the two lisianthus accessions evaluated. Based on these markers, a genetic linkage map was constructed using a breeding population derived from crosses between the two accessions, for which flowering time differed (>140 days when grown under 20°C). We detected one QTL associated with flowering time (phenotypic variance, 27%; LOD value, 3.7). The SSR marker located at this QTL may account for variation in flowering time among accessions (i.e., three accessions whose nodes of the first flower were over 30 had late-flowering alleles of this QTL).

The macroscopic shape of assemblies formed from microparticles based on host-guest interaction dependent on the guest content.

Biological macroscopic assemblies have inspired researchers to utilize molecular recognition to develop smart materials in these decades. Recently, macroscopic self-assemblies based on molecular recognition have been realized using millimeter-scale hydrogel pieces possessing molecular recognition moieties. During the study on macroscopic self-assembly based on molecular recognition, we noticed that the shape of assemblies might be dependent on the host-guest pair. In this study, we were thus motivated to study the macroscopic shape of assemblies formed through host-guest interaction. We modified crosslinked poly(sodium acrylate) microparticles, i.e., superabsorbent polymer (SAP) microparticles, with ß-cyclodextrin (ßCD) and adamantyl (Ad) residues (ßCD(x)-SAP and Ad(y)-SAP microparticles, respectively, where x and y denote the mol% contents of ßCD and Ad residues). Then, we studied the self-assembly behavior of ßCD(x)-SAP and Ad(y)-SAP microparticles through the complexation of ßCD with Ad residues. There was a threshold of the ßCD content in ßCD(x)-SAP microparticles for assembly formation between x = 22.3 and 26.7. On the other hand, the shape of assemblies was dependent on the Ad content, y; More elongated assemblies were formed at a higher y. This may be because, at a higher y, small clusters formed in an early stage can stick together even upon collisions at a single contact point to form elongated aggregates, whereas, at a smaller y, small clusters stick together only upon collisions at multiple contact points to give rather circular assemblies. On the basis of these observations, the shape of assembly formed from microparticles can be controlled by varying y.

Effect of Nd: YAG laser irradiation to the temporomandibular joint on taste threshold.

BACKGROUND/PURPOSE: The tissue absorption laser has been clinically applied to alleviate pain in various areas. It is used for pain relief from temporomandibular disease (TMD) in dentistry. Although the facial and trigeminal nerves are distributed around the temporomandibular joint, the effects of laser irradiation and absorption on the neural functions have not been directly studied. In this study, the Nd:YAG laser was applied to an area where the facial nerve passes with photonic radiation for the treatment of TMD. MATERIALS AND METHODS: Ten volunteers including seven males and three females were selected as subjects. Nd:YAG laser was irradiated area included several internal and external standard and associated acupuncture points. The chorda tympani nerve, a branch of facial nerve is distributed to the front two thirds of the tongue and is associated with the sense of taste. We evaluated the effect of laser irradiation and absorption on the taste function by means of an electric taste meter. RESULTS: No significant difference was identified in the values between before and after laser irradiation (Wilcoxon signed-rank test). CONCLUSION: It was confirmed that there was no effect on taste function while applying Nd:YAG laser irradiation around the TMD joint.

Supramolecular complex formation of polysulfide polymers and cyclodextrins.

We report the first preparation of a supramolecular polysulfide polymer, which is a polyrotaxane containing sulfur-styrene copolymer and methylated α-cyclodextrins (TMαCDs) as linear and cyclic molecules, respectively (SPRx). Compared to the sulfur-styrene copolymer prepared by a copolymerization method typically used to synthesize polysulfide polymers, the environmental and thermal stabilities of SPRx are significantly improved because the polysulfide polymer is covered with TMαCD.

Extremely Rapid Self-Healable and Recyclable Supramolecular Materials through Planetary Ball Milling and Host-Guest Interactions.

The host-guest interaction as noncovalent bonds can make polymeric materials tough and flexible based on the reversibility property, which is a promising approach to extend the lifetime of polymeric materials. Supramolecular materials with cyclodextrin and adamantane are prepared by mixing host polymers and guest polymers by planetary ball milling. The toughness of the supramolecular materials prepared by ball milling is approximately 2 to 5 times higher than that of supramolecular materials prepared by casting, which is the conventional method. The materials maintain their mechanical properties during repeated ball milling treatments. They are also applicable as self-healable bulk materials and coatings, and they retain the transparency of the substrate. Moreover, fractured pieces of the materials can be re-adhered within 10 min. Dynamic mechanical analysis, thermal property measurements, small-angle X-ray scattering, and microscopy observations reveal these behaviors in detail. Scars formed on the coating disappear within a few seconds at 60 °C. At the same time, the coating shows scratch resistance due to its good mechanical properties. The ball milling method mixes the host polymer and guest polymer at the nano level to achieve the self-healing and recycling properties.

Supramolecular Biocomposite Hydrogels Formed by Cellulose and Host-Guest Polymers Assisted by Calcium Ion Complexes.

Hydrogels are biocompatible polymer networks; however, they have the disadvantage of having poor mechanical properties. Herein, the mechanical properties of host-guest hydrogels were increased by adding a filler and incorporating other noncovalent interactions. Cellulose was added as a filler to the hydrogels to afford a composite. Citric acid-modified cellulose (CAC) with many carboxyl groups was used instead of conventional cellulose. The preparation began with mixing an acrylamide-based αCD host polymer (p-αCD) and a dodecanoic acid guest polymer (p-AADA) to form supramolecular hydrogels (p-αCD/p-AADA). However, when CAC was directly added to p-αCD/p-AADA to form biocomposite hydrogels (p-αCD/p-AADA/CAC), it showed weaker mechanical properties than p-αCD/p-AADA itself. This was caused by the strong intramolecular hydrogen bonding (H-bonding) within the CAC, which prevented the CAC reinforcing p-αCD/p-AADA in p-αCD/p-AADA/CAC. Then, calcium chloride solution (CaCl2) was used to form calcium ion (Ca2+) complexes between the CAC and p-αCD/p-AADA. This approach successfully created supramolecular biocomposite hydrogels assisted by Ca2+ complexes (p-αCD/p-AADA/CAC/Ca2+) with improved mechanical properties relative to p-αCD/p-AADA hydrogels; the toughness was increased 6-fold, from 1 to 6 MJ/m3. The mechanical properties were improved because of the disruption of the intramolecular H-bonding within the CAC by Ca2+ and subsequent complex formation between the carboxyl groups of CAC and p-AADA. This mechanism is a new approach for improving the mechanical properties of hydrogels that can be broadly applied as biomaterials.

Self-Healing Thermoplastic Polyurethane Linked via Host-Guest Interactions.

High toughness with self-healing ability has become the ultimate goal in materials research. Herein, thermoplastic polyurethane (TPU) was linked via host-guest (HG) interactions to increase its mechanical properties and self-healing ability. TPU linked via HG interactions was prepared by the step-growth bulk polymerization of hexamethylene diisocyanate (HDI), tetraethylene glycol (TEG), and HG interactions between permethylated amino ßCD (PMeAmßCD) and adamantane amine (AdAm). TPU linked with 10 mol% of HG interactions (HG(10)) showed the highest rupture stress and fracture energy (GF) of 11 MPa and 25 MJ·m-3, which are almost 40-fold and 1500-fold, respectively, higher than those of non-functionalized TEG-based TPU (PU). Additionally, damaged HG(10) shows 87% recovery after heated for 7 min at 80 °C, and completely cut HG(10) shows 80% recovery after 60 min of reattachment at same temperature. The HG interactions in TPU are an important factor in stress dispersion, increasing both its mechanical and self-healing properties. The TPU linked via HG interactions has great promise for use in industrial materials in the near future.

Control of microenvironment around enzymes by hydrogels.

We prepared enzyme-immobilized hydrogels and investigated the effects of the cross-linking density and polymer properties on their oxidation reaction rate. The oxidation rate of enzyme-immobilized hydrogels increased as the cross-linking density in the hydrogels increased. In addition, we controlled the oxidation rate using hydrogels exhibiting an appropriate interaction with a decoy molecule in the hydrogel.

Supramolecular self-healing materials from non-covalent cross-linking host-guest interactions.

The introduction of non-covalent bonds is effective for achieving self-healing properties because they can be controlled reversibly. One approach to introduce these bonds into supramolecular materials is use of host-guest interactions. This feature article summarizes the development of supramolecular materials constructed by non-covalent cross-linking through several approaches, such as host-guest interactions between host polymers and guest polymers, 1 : 2-type host-guest interactions, and host-guest interactions from the polymerization of host-guest inclusion complexes. Host-guest interactions show self-healing functions while also enabling stimuli-responsiveness (redox, pH, and temperature). The self-healing function of supramolecular materials is achieved by stress dispersion arising from host-guest interactions when stress is applied. Reversible bonds based on host-guest interactions have tremendous potential to expand the variety of functional materials.

A palladium-catalyst stabilized in the chiral environment of a monoclonal antibody in water.

We report the first preparation of a monoclonal antibody (mAb) that can immobilize a palladium (Pd)-complex. The allylic amination reaction using a supramolecular catalyst consisting of the Pd-complex and mAb selectively gives the (R)-enantiomer product with an enantiomeric excess (ee) of 98 ± 2%. This is in sharp contrast to the reaction catalyzed by a conventional Pd-catalyst (ee < 2%).

Redox-responsive supramolecular polymeric networks having double-threaded inclusion complexes.

Stimuli-responsive hydrogels have attracted attention as soft actuators that act similarly to muscles. In this work, hydrogel actuators controlled by host-guest interactions have been developed. The introduction of a 1:1 inclusion complex into a hydrogel is a popular design for achieving a change in cross-linking density. To realize faster and larger deformation properties, the introduction of a 1:2 inclusion complex is effective because the alteration in cross-linking density in a hydrogel with 1:2 complexes is larger than that in a hydrogel with 1:1 complexes. A redox-responsive hydrogel actuator cross-linked with 1:2 inclusion complexes is designed, where γ-cyclodextrin (γCD) and viologens modified with an alkyl chain derivative (VC11) were employed as the host and guest units, respectively. γCD includes two VC11 molecules in its cavity. The obtained γCD-VC11 hydrogel cross-linked with the 1:2 complex showed faster and larger deformation behaviour than the αCD-VC11 and the ßCD-VC11 hydrogels cross-linked with a 1:1 complex. The deformation ratio and response speed of the γCD-VC11 hydrogel, which forms a supramolecular cross-linking structure by stimuli, are 3 and 11 times larger, respectively, than those of our previous hydrogel consisting of a ßCD/ferrocene 1:1 inclusion complex.

Development of 'Darumadattan', a semidwarf lodging-resistant Tartary buckwheat cultivar, using gamma-ray irradiation.

We developed a new cultivar of Tartary buckwheat (Fagopyrum tataricum Gaertn.), 'Darumadattan'. This is the first semidwarf Tartary buckwheat cultivar to be developed by mutation breeding using gamma-ray irradiation. In 1999, 100 dry seeds of the leading Japanese cultivar, 'Hokkai T8' (known at that time as 'Hokkei 1'), were gamma-ray-irradiated with a total dose of 500 Gy (25 Gy/h × 20 h) at the Institute of Radiation Breeding (IRB), National Institute of Agrobiological Sciences, Hitachiomiya, Ibaraki, Japan. The seeds were sown in August 1999 in a field at IRB, and M2 seeds were collected from the eight individual plants that survived. In August 2000, 240 M2 seeds were sown in a field, and one semidwarf plant was found. The line named 'IRBFT-20' developed from the selected plant was investigated for its semidwarf characteristic and genetic stability in 2001-2005. 'IRBFT-20' was submitted for registration in 2011 and registered as the cultivar 'Darumadattan' in 2013. This name was chosen because the plants resemble "Daruma dolls" and "dattan" means "Tartary" in Japanese. 'Darumadattan' is a highly lodging-resistant and high-yielding cultivar and is expected to be used as both a commercial cultivar and a crossing parent.

Development of common buckwheat cultivars with high antioxidative activity -'Gamma no irodori', 'Cobalt no chikara' and 'Ruchiking'.

To breed new highly antioxidative common buckwheat cultivars, we selected individual plants from gamma ray-irradiated populations. Selection and propagation were repeated 4 or 5 times. This recurrent selection process resulted in many individuals with enhanced antioxidative activity. Among them, 2 individuals from the forth selection and 9 individuals from the fifth selection were developed into lines with increased antioxidative activities and diverse polyphenolic composition. From these lines, 2 new cultivars 'Gamma no irodori' and 'Cobalt no chikara' were developed. Furthermore, following the selection of individuals with high rutin contents, 'Ruchiking' was developed.

Atroposelective antibodies as a designed protein scaffold for artificial metalloenzymes.

Design and engineering of protein scaffolds are crucial to create artificial metalloenzymes. Herein we report the first example of C-C bond formation catalyzed by artificial metalloenzymes, which consist of monoclonal antibodies (mAbs) and C2 symmetric metal catalysts. Prepared as a tailored protein scaffold for a binaphthyl derivative (BN), mAbs bind metal catalysts bearing a 1,1'-bi-isoquinoline (BIQ) ligand to yield artificial metalloenzymes. These artificial metalloenzymes catalyze the Friedel-Crafts alkylation reaction. In the presence of mAb R44E1, the reaction proceeds with 88% ee. The reaction catalyzed by Cu-catalyst incorporated into the binding site of mAb R44E1 is found to show excellent enantioselectivity with 99% ee. The protein environment also enables the use of BIQ-based catalysts as asymmetric catalysts for the first time.